Shape Memory Alloys. [1] Hodgson DE, Wu MH & Biermann RJ (1990). Shape Memory Alloys, Metals Handbook. Vol. 2. ASM International, Ohio,

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1 Shape Memory Alloys Metals are characterized by physical qualities as strength, ductility and conductivity. Shape memory alloys (SMA) constitute a group of metallic materials with the ability to recover a previously defined length or a shape when subjected to an appropriate thermo-mechanical load [1]. When there is a limitation of shape recovery, these alloys promote high restitution forces. [1] Hodgson DE, Wu MH & Biermann RJ (1990). Shape Memory Alloys, Metals Handbook. Vol. 2. ASM International, Ohio,

2 Pseudoelastic and shape memory effects are some of the behaviors presented by these alloys. Although a relatively wide variety of alloys present the shape memory effect, only those that can recover from a large amount of strain or generate an expressive restitution force are of commercial interest. Examples are Ni-Ti, Cu-Zn-Al and Cu-Al-Ni [1]. Basically, SMAs present two well-defined crystallographic phases, i.e., austenite and martensite. The high temperature phase, austenite is named after English metallurgist William Chandler Austen, and the low temperature phase, martensite is named after German metallographer Adolf Martens. The shape memory is a particular manifestation of a crystalline phase transformation known as the Martensitic Phase Transformation. The martensitic phase transformation is a solid-to-solid phase transformation where the lattice or molecular structure changes abruptly at some temperature.

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4 Twinning Twinning is the coordinated motion of planes of atoms in a lattice parallel to a specific plane (the twinning plane) such that the lattice is divided into two symmetrical parts possessing the same crystal structure, but which are a mirror image of each other.

5 Crystallography of Twinning

6 Twinning occurs in many structures, for example: Hexagonal metals such as Zn and Mg twin when they are deformed at ambient temperatures. BCC metals such as Fe twin when they are deformed at sub-ambient temperatures.

7 Taken from the book by H. K. D. H. Bhadeshia Professor of Physical Metallurgy University of Cambridge Mathema'cal Crystallography FCC BCT BCC

8 Consider a vector u which can be wriden as a linear combina@on of the basis vector A The components of u can be wriden as a single row matrix or as a single column matrix The row matrix is the transpose of the column matrix Consider an alterna@ve basis a body centred tetragonal (BCT) unit cell describing the same austenite lajce. It is obvious that And the equa@ons that relate the transforma@on of a vector u are

9 This 3x3 matrix the co ordinate is denoted as (B J A) and transform the components of vector referred to the A basis to those referred to the B basis. The components of a vector u can now be transformed between bases using the matrix (B J A) as follows In the example:

10 Example 1: Two adjacent grains of austenite are represented by basis A and B. The grains are oriented such that Angle of 45 degrees as shown If a vector in the crystal A is given by Find the same vector in basis B Note that the components of (B J A) are the cosines of angles between b i and a j

11 We must return to the of martensite, and how a homogeneous deforma@on might transform the austenite lajce (parameter aγ) to a BCC martensite (parameter aα). Referring to the figure, the basis A is defined by the basis vectors ai, each of magnitude aγ, and basis B is defined by basis vectors bi. Focusing aden@on on the BCT representa@on of the austenite unit cell, it is evident that a compression along the [0 0 1]B axis, coupled with expansions along [1 0 0]B and [0 1 0]B would accomplish the transforma@on of the BCT austenite unit cell into a BCC α cell. This deforma@on, referred to the basis B, can be wriden as: Along the [100]B and [010]B Along the [001]B

12 Imagine that a part of a single crystal of austenite undergoes the prescribed deforma@on, allowing us to describe the strain in terms of the remaining (and undeformed) region, which forms a fixed reference basis. Hence, the deforma@on matrix does not involve a change of basis and the transforma@on will be given by a 3x3 matrix (A S A). (A S A) converts a vector u in basis A into a new vector v s@ll in basis A. A major advantage of the Mackenzie Bowles nota@on is that it enables a clear dis@nc@on to be made between 3X3 matrices which represent changes of axes and those which represent physical deforma@ons referred to one axis system.

13 Example 2: Given that the principal of the Bain strain (A S A), referred to the crystallographic axes of the FCC γ lajce (lajce parameter aγ), are η1 = η2 = , and η3 = , show that the vector [A; x] = [ ] remains undistorted, though not unrotated as a result of the opera@on of the Bain strain. Furthermore, show that for x to remain unextended as a result of the Bain strain, its components x i must sa@sfy the equa@on Solu'on: As [A;y] is not a mul@ple of [A;x] then these two vectors are not parallel, hence y rotates due to the Bain strain

14 Consider the magnitude of the two vectors. If equal the vectors are undistorted due to the Bain strain.

15 This process can be illustrated by considering a spherical volume of the original austenite lajce; (A S A) deforms this into an ellipsoid of revolu@on Note that the principal axes (ai) remain unrotated by the deforma@on, and that lines such as ab and cd which become a b and c d respec@vely, remain unextended by the deforma@on (since they are all diameters of the original sphere), although rotated through the angle θ.

16 Suppose now, that the ellipsoid from the Bain strain is rotated through a right handed angle of θ, about the axis a2. This rota@on will cause the ini@al and final cones of unextended lines to touch along cd, bringing cd and c d into coincidence. If the total deforma@on can therefore be described as (A S A) combined with the above rigid body rota@on, then such a deforma@on would leave the line cd both unrotated and unextended; such a deforma@on is called an invariant line strain. No@ce that the total deforma@on, consis@ng of (A S A) and a rigid body rota@on is no longer a pure strain, since the vectors parallel to the principal axes of (A S A) are rotated into the new posi@ons a I. (martensite transforma@on must contain an invariant line)

17 Interfaces The η of its final to length is called a principal deforma@on associated with that principal axis and the corresponding quan@ty (η 1) is called a principal strain. When two of the principal strains differ in sign from the third (all nonzero), it is possible to obtain a total strain which leaves one line invariant. When the invariant line is at the interface of the two crystals then their lajces would match exactly along that line. A completely undistorted interface would have to contain two nonparallel direc@ons which are invariant to the total transforma@on strain (invariant plane strain a plane that remains unrotated and undistorted).

18 Example 3: A pure strain (Y Q Y), referred to an orthonormal basis Y whose basis vectors are parallel to the principal axes of the deforma@on, has the principal deforma@ons η 1 = , η 2 = 1 and η 3 = Show that (Y Q Y) combined with a rigid body rota@on gives a total strain which leaves a plane unrotated and undistorted. η2 = 1 > ef//y2 It remains unextended and unrotated Transform and rotate about y2 (ef) then cd will remain unrotated and undistorted. Any combina@on of ef and cd will also remain invariant

19 Thus, a pure strain when combined with a rigid body rotaoon can only generate an invariant plane strain only if two of its principal strains have opposite signs, the third being zero. Since it is the pure strain which actually accomplishes the lajce change (the rigid body rota'on causes no further lajce change), any two lajces related by a pure strain with these characteris'cs may be joined by a fully coherent interface. The (Y Q Y) transformaoon matrix represents the pure strain part of the total transformaoon strain required to change a FCC lauce to an HCP lauce, without any volume change, by shearing on the (1 1 1)γ plane in the [1 1 2]γ direcoon. The magnitude of the shear being equal to half the twinning shear.

20 Example 4: The Bagaryatski Orienta'on Rela'onship (θ) has an orthorhombic crystal structure, with lajce parameters aθ = , b = and c = Angstroms along the [1 0 0], [0 1 0] and [0 0 1] direc@ons respec@vely. When cemen@te precipitates from ferrite (α, BCC structure, lajce parameter aα = A), the lajces are related by the Bagaryatski orienta@on rela@onship, given by: Derive the co ordinate transforma@on matrix (α J θ) represen@ng this orienta@on rela@onship Solu'on: The orienta@on rela@onship denotes parallelism between vectors in the two lajces. To find (α J θ) it is necessary to ensure that the magnitudes of the parallel vectors are also equal, since the magnitude must remain invariant to a co ordinate transforma@on.

21 By if we the [0 1 1]α by k then we should obtain the direc@on [1 0 0]θ. Each column of (α J θ) represents the component of a basis vector of θ in the α basis. A general expression for finding (α J θ) is

22 Martensitic Transformations Suppose that the atoms in the solid are arranged in a square lattice at high temperature. During cooling there will be a thermal contraction, but when a critical temperature is reached, the crystal lattice structure changes abruptly to the rectangular lattice. Though the distortion of the cell is significant, there is no diffusion and there is not change in the relative position of the atoms during the transformation.

23 The martensitic transformation is displacive (no diffusion) and first order (abrupt change in lattice parameter). When heated back, it reaches another critical temperature and the crystal structure abruptly changes from the rectangular lattice to the square lattice. Therefore the transformation is crystallographically reversible. The high temperature phase is known as austenite phase and the low temperature phase is the martensite phase.

24 Martensite is a phase that, in the absence of stress, is stable only at low temperatures; in addition, it can be induced by either stress or temperature. Martensite is easily deformed, reaching large strains (~8%) [1].

25 The martensitic transformation is shear-dominant diffusionless solid-state phase transformation occurring by nucleation and growth of the martensitic phase from the parent austenitic phase [2] [2} Olson, G.B., Cohen, M., Stress assisted isothermal martensitic transformation: application to TRIP steels ; Metall. Trans. A 13, Martensitic transformations are displacive, diffusionless transformations during which the atoms execute a small, well-defined and cooperative movement, resulting in a change in lattice structure and a shape change. The lattice structure of the resulting martensite has an orientation relationship to the lattice structure of the parent phase. The martensite phase is separated from the parent phase by an undistorted plane, called the habit plane.

26 Habit plane The martensitic phase takes the form of plates or needles, which appear to be embedded in the matrix along certain well-defined planes. Such a plane, the plane of contact between the two phases or interface plane, is called the habit plane. It separates the parent and martensite phases. In the figure above the planes EFIJ and GHKL are habit planes.

27 The habit planes which occur in a specimen don t have arbitrary directions, owing to the well-defined movements of atoms during transformation. These directions are specified by indices of planes in the parent phase. Two important features of habit planes; the habit plane is essentially an undistorted plane and the habit plane must also be unrotated.

28 Lattice Correspondence Since the martensitic transformation occurs diffusionlessly, the lattice of the parent phase deforms to that of the martensite phase maintaining one-to-one correspondence. The Bain deformation results in the following correspondence of crystal planes and directions between the parent and the product phase: But in fact, the experimental observed orientation relationships are irrational. The relative directions can vary between <101>γ // <111>α (the Kurdjumov- Sachs relationship) and <110>γ // <101>α (the Nishiyama-Wasserman relationship) and these two orientation differ by ~5º about [111] γ.

29 It can be derived that the direction [100] f becomes the direction [110] b (the subscripts f and b refer to the fcc and bct structures respectively), [0l0] f becomes [-110] b and [001] f becomes [001] b. This implies that the following lattice correspondence: The matrix is called correspondence matrix, and belongs to the described Bain correspondence; if another correspondence is assumed to transform a fcc into a bct lattice, then another correspondence matrix results.

30 Tetragonal martensite in Fe-Ni alloys has a c/aratio of 1.0, while in the parent structure this ratio is 2. If the volume of the structural cell doesn't change during transformation (which is true for NiTi), then the following principal distortions are obtained: A clear view of this deformation can be obtained by considering a unit sphere in the parent structure, just as the transformation occurs from cubic to tetragonal to tetragonal then the sphere transforms into an ellipsoid.

31 The ellipsoid intercepts the sphere in two circles (with x 3 as axis), namely the A -B and C -D. The cones given by OA, OB, OC, and OD represent positions in the parent and martensite that have no change dimensions. There is no-plane that it is undistorted only two cone-vectors are unchanged in length. Hence, the Bain model describes the change in lattice structure but it is inconsistent with an important feature of the martensitic transformation an almost undistorted habit plane.

32 The condition of an almost undeformed plane, the habit plane is satisfied by a second deformation in the form of a simple shear. A sphere is sheared on an equatorial plane K 1 in the direction d. All points of the structure are displaced in the direction of d the distance over which a point is displaced is proportional to the distance of the point to the shear plane K 1.

33 As a result of the shear, any vector in the plane AK 2 B is transformed into a vector in the plane AK 2 B; its magnitude is unchanged, the vector is only rotated. All vectors on the left of AK 2 B are decreased in length, those on the right are increased. The plane AK 2 B represents the initial position of the plane AK 2 B which remains undistorted as a result of shear. Obviously, the relative positions of the planes AK 2 B and AK 2 B depend upon the amount of shear: the bigger the shear, the bigger angle α.

34 Combining Bain Distortion and Simple Shear Combining these two effects leads to the following conclusion: a simple shear (of a unique amount, on a certain plane, and in a certain direction) can be found such that vectors which are increased in length due to the Bain lattice deformation are correspondingly decreased in length by the same amount due to the simple shear, and vice-versa. Such vectors which remain invariant in length to these operations define potential habit planes. The simple shear can be either a slip shear or a twinning shear (later more), but in either case, the lattice is left invariant, and the simple shear is thus termed a lattice invariant shear, which may be represented by a matrix P. B matrix deformation due to Bain model P matrix deformation due to slip shear or twinning shear

35 Rigid body rotation: The third additional requirement that the habit plane be unrotated as well has not yet been fulfilled. If in addition to the lattice deformation and the lattice invariant deformation, a rigid body rotation (about a certain axis, over a unique amount θ) is supposed to return the undistorted plane to its original position, then an undistorted and unrotated plane will exist. This rotation can be described by means of a matrix R.

36 Total Shape Change: The features of the total macroscopic shape change, i.e. surface relief and an undistorted and unrotated habit plane, match well to a mathematical model called invariant plane strain (IPS). Then, the displacement of any point is in a common direction and proportional to the distance from a fixed (i.e., not moved by the strain) plane of reference, which is the invariant plane. Simple examples are simple shear and uniaxial extension. A general IPS can be represented by the combination of these two, where a martensite plate is formed within a single crystal of the parent phase. The invariant plane is of course the habit plane.

37 The total shape change may also be described by means of three subtransformations, with respective matrices B, P and R. Therefore we can write: B matrix deformation due to Bain model P matrix deformation due to slip shear or twinning shear R matrix Rigid body rotation B can be determined by XRD by calculating the lattice parameters of the parent and martensite phases. P can be determined by making assumptions on the direction and shear plane for the lattice invariant strain. The matrix F determines the habit plane. Two possible solutions.

38 R can be calculated from the condition that the habit plane (with a unit plane normal p t, is unrotated. If the equation is applied to p t The amount of shear m t and the shear direction d t can be calculated. The fcc + bct transformation that occurs in steel is used as example. However, most SMA's have a bcc structure in the high temperature state, which transforms into some other structure. The phenomenological theory described above is likewise applicable to any other martensitic transformation.

39 Martensitic Transformation Martensitic transformations are diffusionless, the change in crystal structure being achieved by a deformation of the parent phase. As in mechanical twinning, there is an invariant plane on which there is a shear; the transformation may also involve a volume change which occurs normal to the invariant plane. c.c.p. h.c.p. e.g. cobalt To transform a c.c.p. structure into h.c.p. requires a displacement of a/6 < > on every second {1 1 1}ccp ( )hcp. The latter is the invariant plane. FCC HCP transformation

40 c.c.p. b.c.c. e.g. iron The deformation necessary to convert the c.c.p. structure into b.c.c. is more complicated than the simple shear of the previous example. There is a compression along the z axis and a uniform expansion along the x and y axes. Bain strain.

41 What make SMAs different from other materials are primarily the shape memory effect (SME) and pseudoelasticity, which are associated with the specific way the phase transformation occurs. When a SMA undergoes a martensitic phase transformation, it transforms from its high-symmetry, usually cubic austenitic phase to a low-symmetry martensitic phase, such as the monoclinic variants of the martensitic phase in a NiTi SMA.

42 In the absence of applied stresses, the variants of the martensitic phase usually arrange themselves in a self-accommodating manner through twinning, resulting in no observable macroscopic shape change. By applying mechanical loading, the martensitic variants are forced to reorient (detwin) into a single variant leading to large macroscopic inelastic strains. After heating above certain temperature, the martensitic phase returns to the austenitic phase, and the inelastic strains are recovered. This behavior is known as the SME.

43 Slip or Twinning It has been stated that the required shear deformation (matrix P) can be produced by either slip or twinning. Due to the lattice deformation (Bain Distortion), the parent phase lattice is changed to the martensite lattice, resulting in a certain shape change (solid line). The observed shape change of the crystal is different, indicated with the dashed line. The dashed line in (c) and (d) marks the habit plane, the plane which separates the parent and martensite phase. Comparison of (b) with (c) and (d) makes clear that slip or twinning is necessary to connect the parent and martensite phase along the habit plane.

44 The interface between the austenite and martensite is called the habit plane How does the martensite grows in an austenitic matrix? the lattice distortion makes them incompatible. Single martensite with slip (irreversible process) Twin martensite variants (reversible process)

45 When slip occurs in a crystal, then crystal planes glide over each other (usually close packed planes in close packed directions). This process is irreversible; it is not possible to return the crystal into its exact original configuration. Martensitic transformations which are accompanied by slip are therefore irreversible transformations and metals or alloys with this property cannot show the SME, since a reversible martensitic transformation is required. Crystal structures which possess very little slip possibilities, have a quite different mechanism to react on shear loads: twinning. When twinning occurs, atoms in a thin band move over a distance, which is less than an interatomic distance, in such way, that afterwards the atoms are mirrored-about a mirror plane, called the twinning plane. The thin band is bounded by two parallel twinning planes. Twins occurring during deformation are found in all metal lattices. They are formed either because the deformation takes place so rapidly that the usual deformation process doesn t occur or because the normal plastic deformation is difficult to be brought about; this is the case when the stress, needed to cause the turning over, is less than the stress giving rise to plastic deformation by slip.

46 Twinned Martensite Microstructure A twin in a crystalline solid occurs between two adjacent regions of the same crystal lattice, where one of the regions is related to the other by a simple shear. The dashed line shows two unit cells of the original lattice before the shear; while, the solid line indicates a unit cell for each of the lattices after the shear. A twin is also defined by its twinning elements, η 1, κ 1, η 2, κ 2 and, some of which are shown. Specifically, the twin plane normal is parallel to κ 1 ; the direction of the twin shear is parallel to η 1 ; a second undistorted plane has normal κ 2 ; and an undistorted vector in this previous plane is parallel to η 2. The magnitude of the twin shear is s.

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48 Twinning is a reversible process. That is why martensites formed in SMA s are often internally twinned. It should be noted that the important parameter in twinned martensite is the proportion of the twinned volume to the untwinned volume, i.e. the relative thicknesses of the bands determine the amount of macroscopic shear.

49 How does martensite grow under an imposed shear like deformation? Austenite initially transforms to twinned martensite, which in turn gives way to a single variant martensite (detwinning).

50 Ni-Ti-NOL (Navy Ordinance Laboratory) The NiTi Nitinol is a commonly used shape memory alloy. It corresponds to an stoichiometry Ni 50 Ti 50. It has a B2 (CsCl crystal structure) which forms directly from the liquid and it is stable at room temperature. It is an ordered alloy.

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52 Martensite Variants When a martensitic transformation occurs, the external shape of the specimen changes significantly. In reality such drastic shape change is not observed at the macro-scale. This is because of the following: 1. The parent phase is often not a single crystal, but polycrystalline. A lot of grains with different orientations exist in a polycrystalline material. This will cause constraining effects at the grain boundaries; if a particular grain wants to change its shape, then the surrounding grains prohibit this shape change to a large extent. 2. Even when we are dealing with a parent phase consisting of a single crystal, still no macroscopic shape change will occur. This is due to the formation of so-called martensite variants.

53 Formation of Martensite Variants Crystallographic Features Most SMA s have basically superlattices with bcc structures in the high temperature state. Alloys with bcc structures are classified as, β phase alloys. Regardless of the type of alloy, β phases of alloys which have about 50:50 composition ratios (like NiTi) and are ordered like CsCl are denoted by β 2 or B2. β phases of alloys which have about 75:25 composition ratios and are ordered like Fe 3 Al are denoted by β 1 or DO 3. In front of the page

54 The B2 structure could be viewed as a result of alternatively stacking the planes (b) and (c), giving an FCT cell. It is thought that the martensitic transformations which occur in B2 phase alloys are due to: (I) an orthorhombic distortion, resulting in different values of the lattice parameters, but still right angles; (II) shearing, which is for NiTi in the [011]B2 direction along the (100)B2 plane, and (III) a planar shuffle: the atoms in alternate (011)B2 planes shift about 1/3 in the [ 01-1] direction.

55 Variants in NiTi Above the (100) plane was taken as the shear plane; however, crystallographically equivalent structures can be obtained by shearing in the (010) and (001) planes. The same holds for the shear directions. The conclusion is that even though the parent phase consists of a single crystal, a number of different martensites, i.e. with different lattice correspondences and with different habit plane indices (but nonetheless crystallographically equivalent), will appear scattered throughout the specimen. These martensites with different habit plane indices are called variants. In BCC SMA s, 24 variants are possible. These 24 variants do not come into existence randomly.

56 The number designation of each habit plane variant indicates the dominant (major) correspondence variant: variant 1 or 1 is more dominantly present then variant 2, while variant 6 and 6 are minor variants. The same number appears with and without a prime ( ); this indicates that the pair are variants with oppositely directed shears. Finally, for a given shear plane and direction, there are two possible solutions for the habit plane indices, this is indicated by a (+) and (-).

57 What happens if an external stress is applied? There are two different situations: 1. the starting material consists of a single twinned martensite plate, i.e. only one variant (dashed lines). By applying a shear stress, the internal interfaces, mostly twin boundaries, will move. One of the two twin variants will shrink (2) while the other (1) is growing resulting in the shown macroscopic shape change. On further stressing, eventually the plate will be totally detwinned, and plastic deformation like slip will commence.

58 2. the material consists of several variants, which is an idealized situation, where two out of the twenty-four martensite plate variants have grown together as a self-accommodating martensite plate group in order to minimize the strains and stresses. The parent phase above and below the martensite plates is kept fixed. If the sample is not kept fixed but strained by a shear stress, the martensite plate group tends to minimize the internal stresses by changing the amount of the two variants present. This means that the boundary CD between the two martensite plates moves or that the habit plane AB moves faster than the habit plane EF. So in this case certain variants grow at the expense of others by means of moving interfaces, and eventually only one variant persists (after which (1.) may occur). This process is called reorientation of martensite variants.

59 Reverse Transformation An important feature of the Shape Memory Effect is that on heating the specimen regains its original macroscopic form.

60 In the figure there are, three equivalent lattice correspondences, represented by the rectangles marked A, B and C. If the reverse transformation occurs along path A, then the crystal structure of the product phase will be as shown in (b), and the B2 superlattice structure of the parent phase will be preserved in both the forward and reverse transformations. However, if it occurs along either the B or C paths, the resultant crystal structure will be as shown in (c) (markedly differ from the original B2 structure). The latter structure shown in (c) would raise the free energy, reverse transformations along path B or C are impossible. Thus the orientation of the parent phase crystal is automatically preserved by its ordered structure.

61 Temperature Behavior of the Martensitic Transformation The transformation temperature is the temperature at which a SMA changes from Austenite to Martensite or vice-versa. For any particular alloy chemistry, the transformation temperature can be changed by the processing history, and the stress conditions. Although for practical purposes a single transformation temperature can be used, the picture is somewhat complicated by hysteresis.

62 All the deformation up to about 8% is elastic or in other words it can be recovered, but not by simply relaxing the stress whilst in the martensitic condition. The higher temperature austenitic structure has the characteristic stress-strain curve of most metals. The lower temperature martensitic structure has a stress-strain curve more like that of an elastomer in which there is a plateau in the stress/strain curve.

63 Martensitic transformations are usually divided into two groups thermoelastic and non-thermoelastic. The non-thermoelastic transformations occur mainly in ferrous alloys and are associated with non-mobile martensite-parent phase interfaces pinned by permanent defects and proceed by successive nucleation and growth. Due to re-nucleation of austenite during the reverse (martensite to austenite) transformation, these transformations are crystallographically non-reversible in the sense that the martensite cannot revert to the parent phase in the original orientation. The thermoelastic martensitic transformations, on the other hand, are associated with mobile interfaces between the parent and martensitic phases. These interfaces are capable of backward movement during the reverse transformation by shrinkage of the martensitic plates rather than nucleation of the parent phase, which leads to a crystallographically reversible transformation (Otsuka and Wayman, 1999). The unique properties of SMAs (i.e., shape memory effect, pseudoelasticity) are the result of thermoelastic martensitic transformation.

64 Thermoelasticity: The thermoelastic transformation is a transformation in which a given plate or domain of martensite grows or shrinks as the temperature is respectively lowered or raised, and the growth rate appears to be governed only by the rate of change in temperature. The first observed and most well-known martensitic transformation occurs during the hardening of steel. In pure iron, the austenitic fcc lattice transforms into a bcc lattice. In quenched steel (Fe-C alloy), this transformation is prevented by the carbon atoms dissolved in the fcc lattice of iron. The structure that results is the martensite bct structure. The quenching is essential to prevent diffusion of C atoms out of the fcc lattice to form cementite (Fe 3 C). This clearly shows the diffusionless character of the martensitic transformation. However, short distance diffusions, which always occur, and diffusion during heating cause the irreversibility of the martensitic transformation in steel. This kind of transformation is obviously non- thermoelastic.

65 NiTi does show thermoelastic behaviour. Quenching is not needed to achieve a martensitic transformation: the transition from a B2 to a B19 lattice also takes place during slow cooling near room temperature. Summarized below are the main characteristics of martensitic phase transformations: It is associated with an inelastic deformation of the crystal lattice with no diffusive process involved. It results from a cooperative and collective motion of atoms over distances smaller than the lattice parameters. The absence of diffusion makes the martensitic phase transformation almost instantaneous (Nishiyama, 1978). Parent and product phases coexist during the phase transformation, since it is a first order transition, and as a result there exists an invariant plane, which separates the parent and product phases. The lattice vectors of the two phases possess well defined mutual orientation relationships (the Bain correspondences, see Bowles and Wayman, 1972), which depend on the nature of the alloy.

66 Transformation of a unit cell element produces a volumetric and a shear strain along well defined planes. The shear strain is many times larger than the elastic distortion of the unit cell. This transformation is crystallographically reversible (Kaufman and Cohen, 1958). Since the crystal lattice of the martensitic phase has lower symmetry than that of the parent austenitic phase, several variants of martensite can be formed from the same parent phase crystal (De Vos et al., 1978). Stress and temperature have a large influence on the martensitic transformation. Transformation takes place when the free energy difference between the two phases reaches a critical value (Delaey, 1990).

67 Pseudo Elasticity or Superelasticity Pseudo-elasticity occurs in SMAs when the alloy is completely composed of Austenite (temperature is greater than Af). Unlike the shape memory effect, pseudo-elasticity occurs without a change in temperature.. The load on the shape memory alloy is increased until the Austenite becomes transformed into Martensite simply due to the loading. The loading is absorbed by the softer Martensite, but as soon as the loading is decreased the Martensite begins to transform back to Austenite since the temperature of the alloy is still above Af, and the wire springs back to its original shape

68 Some examples of applications in which pseudoelasticity is used are: Eyeglass Frames Brassieres Underwires Medical Tools Cellular Phone Antennae Orthodontic Arches

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70 Pseudoelasticity is observed when the martensitic phase transformation is induced by applied thermomechanical loading of the austenitic phase in which case detwinned martensite is directly produced from austenite. The process is associated with large inelastic (transformation) strains which are recovered upon unloading due to the reverse phase transformation (Wayman, 1983).

71 Capability for so called "constant force" action on the strain of up to 6% results in wider and wider application of orthodontic wires made of NiTi.

72 Shape Memory Effect We cool the material and it becomes martensitic. It does not change shape by being cooled, but we can now deform it mechanically. If it stays cold it will remain deformed, but if we allow it to warm up, the austenitic structure reappears and the material returns to its original shape. This cycle from austenitic to martensitic to deformed martensitic and back to austenitic is repeatable indefinitely and is what we call free recovery. It is important to note that it is a One-Way process, we can only go around clockwise.

73 AB BC CD DE AB Austenite is cooled and it transform into martensite with many twinning variants. BC - At low temperature, the material is deformed. The martensite with many variants is detwinned because it is subjected to stresses. CD The stresses are eliminated DE The detwinned martensite transforms into austenite and it recovers its previous shape.

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76 Free recovery mode of operation Shape memory alloy materials can perform work similarly to standard heat engines. Low temperature High temperature Work= Weight*Stroke High temperature (austenite curve) Heating Stress Low temperature (martensite curve) Strain

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81 Functional Properties of Shape Memory Alloys SMAs have different shape-memory effects and can be used in different ways. One-Way Shape-Memory Effect A shape memory element can be deformed in its martensitic state to almost any cold shape. The basic restriction is that the deformations may not exceed a certain limit, typically 8%. These apparent plastic deformations can be recovered completely during heating when the reverse transformation occurs and results in the original hot shape. This strain and shape recovery during heating is called the one-way shape-memory effect because only the hot shape is memorized.

82 Physical basis for this one-way effect (reverse martensitic transformation): 1. The preferential orientation of the martensitic variants originates from the application of stress (below Mf). 2. The reverse transformation to the parent phase during heating is accompanied by a strain and shape recovery. 3. The one-way shape-memory effect is thus a property inherent in the reversible, thermoelastic martensitic transformation. 4. The preferential orientation of the martensitic variants can also be obtained during the forward transformation that causes preferentially oriented formation of martensite. Thus, the apparent plastic strain is caused by the preferential orientation of martensite.

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84 Two-way Shape Memory Effect Shape memory effect normally describes the one-way shape memory effect, where an externally applied load is required to promote de-twinning and/or reorientation of the martensite variants so that a new deformed shape can be obtained and recovered upon heating above Af. Subsequent cooling from the austenite to the martensite phase does not induce large strains i.e. new shape. If large transformation strains are generated during both heating and cooling of the material, then this property is known as the two-way shape memory effect and was observed for the first time by Perkins (1974). The two-way shape memory is not an intrinsic but an acquired characteristic. It can be obtained by cyclic repetition of certain thermomechanical loading paths.

85 Two-Way Shape-Memory Effect and Training The two-way memory effect involves memorization of two shapes. The figure shows that a cold shape is obtained spontaneously during cooling. Different from the one-way memory effect, no external forces are required to obtain the memorized cold shape. During subsequent heating, the original hot shape is restored. The maximum strains are in general substantially smaller than those of the one-way memory effect. A strain limit of about 2% has been mentioned, although higher TWME strains have been found in specific cases.

86 Typically, there are two training procedures (23): thermal cycling with constant stress and thermal cycling with imposed strain. Both induce considerable plastic strains.

87 Thermal Cycling with a Constant Stress When a constant stress (e.g. torsion τ), which is insufficient to induce the martensite, is applied at a temperature T >Af, then during cooling the Ms temperature is attained for one particular variant, giving rise to a large strain γ. On heating the specimen will ordinarily return into its austenitic state. When such thermal cycles are repeated a number of times (N>10 to stabilize the hysteresis loop), it is consequently observed that, without any external applied stress, a spontaneous strain occurs in the same direction as with the stress; its amplitude depends on the number of cycles and on the applied stress during training. This type of training is the most efficient one. It also allows to predict the high and low temperature shapes with good accuracy.

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89 Thermal Cycling with Imposed Strain The sample in the austenite state is submitted to an elastic strain in such a way that the corresponding elastic stress is not enough to generate martensite or plasticity. By cooling the stress induces the favored variants; this relaxes the stress itself because the strain remains constant. On further cooling the sample strain surpasses the imposed strain, which is a proof that the favored variants, once created, carry on to increase even with zero stress. By heating, the sample recovers its initial shape and stress. When this cycle is repeated a number of times, it will also lead to the TWME, but with less efficiency than the former method.

90 Physical basis for the TWME (two-way memory effect): 1. This spontaneous shape change was observed only after particular thermomechanical procedures. 2. These thermomechanical procedures (training) are in general based on the repetition of thermomechanical cycles through the transformation region (73,76,79), that consists of transformation cycles from the parent phase to preferentially oriented martensite. 3. It is generally agreed that cyclic training procedures generate some kind of microstructural asymmetry in the parent phase (texture), so that preferential martensitic variants are formed in subsequent thermal cycles, thus causing the TWME (76,82). 4. The one-way shape-memory effect is thus a property inherent in the reversible, thermoelastic martensitic transformation. 5. The preferential orientation of the martensitic variants can also be obtained during the forward transformation that causes preferentially oriented formation of martensite. Thus, the apparent plastic strain is caused by the preferential orientation of martensite.

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92 Applications Despite great scientific efforts to understand, improve and practically use Shape Memory Alloys, only two alloys presently suitable enough for wide spread applications: NiTi and CuZnAl.

93 Constrained recovery applications Industrial applications in which the SME is used only once are for instance tubing or pipe couplings. In these products a NiTi (or ~ Cu-based) alloy which has a transformation temperature far lower than room temperature (about -150 C) is formed into tubing with an inner diameter about 4% smaller than the nominal outer diameter of the pipes to be joined. When the connection is to be made, the coupling is first immersed in liquid nitrogen and maintained in a low (martensite) state; then a tapered plug is forced inside the coupling so that its inner diameter is expanded by about 7-8%. While keeping the coupling at the low temperature, the two pipes are inserted at both ends of the coupling. When the coupling s temperature rises to room temperature, its inner diameter reverts to the size before the expansion, and the ends of the two pipes are strongly bound together.

94 Actuators For actuators a two way operation is needed. There are two methods for achieving two-way operation properties: - induce the TWME by training processes; since this is still a rather difficult matter, it has not been used yet extensively. - combine a OWME alloy with springs, weights, or other parts so that the component as a whole has two way characteristics.

95 A simplified actuator shown is of the so-called bias-type: it consists of a shape memory coil and an ordinary coil spring. The point where the load on the SMA coil is zero is the origin; the zero load point of the coil spring is 50 mm to the left. At room temperature, the SMA follows the lower force-deflection curve and an equilibrium sets in at 34mm from the origin. When the SMA coil is heated above Af, it stiffens so that the upper graph is valid: the equilibrium is disturbed and a displacement of 18mm is obtained. If the actuator is used to perform external work, the stroke length is effectively shortened; if for example a force of 0.5N works opposite to the displacements at both high and low temperatures, the stroke length would be reduced to 10mm. The stroke may be extended by utilizing rotational movements and moments.

96 Heat engines A special application which uses the ability to do work by means of recovery forces is the heat engine. The principle is as follows: below Mf the martensitic specimen is deformed by means of a relatively small force. This force is replaced by a large force. On heating large recovery stresses occur doing external work. The large force is again replaced by the smaller one, after which the temperature is lowered; the cycle is completed.